Bis (3,4,4-trifluoro-3-butenyl) sulfide as a nematocide

ABSTRACT

Certain trifluorobutenyl compounds of the formula

United States Patent [151 3,692,912 Brokke [451 Sept. 19, 1972 [s41 BIS (3,4,4-TRIFLUOR0-3-BUTENYL) OTHER PUBLICATIONS SULFIDE AS A NEMATOCIDE Mervin E. Brokke, Richmond, Calif.

Staufier Chemical Company, New York, N.Y.

Filed: Nov. 20, 1969 Appl. No.: 877,540

Related US. Application Data Division of Ser. No. 490,664, Sept. 27, 1965, Pat. No. 3,513,172.

Inventor:

Assignee:

US. Cl. ..424/335, 424/251, 424/263,

- 424/270, 424/274, 424/300 Int. Cl. ..A0ln 9/12 Field of Search....424/335; 260/608, 609 A, 302

References Cited 0 UNITED STATES PATENTS 12/ l 965 Brokke ..260/25l 5/1970 Brokke ..260/302 Chemical Abstracts 55:209l4b (1961) Primary ExaminerAlbert T. Meyers Assistant Examiner-Leonard Schenkman Attorney-Wayne C. Jaeschke and Edwin H. Baker [57] ABSTRACT Certain trifluorobutenyl compounds of the formula wherein R is a member selected from the group consisting of chlorothiophenyl, thio 3,4,4-trifluoro-3-butenyl, 2-thio-4,4,6-trimethyldihydropyrimidyl, 2- thiobenzoxazoyl, 2-thiobenzothiazolyl, 2-thio-4-alkylthiazolyl, S-(3,4,4-trifluoro-3-butenyl) -ethylene-bis (dithiocarbamoyl), thiobenzyl, thionaphthyl, phthalimido, dithio-3,4,4-trifluoro-3-butenyl, thiopyridyl, N-thiazolidyl dione and 5-thio-3-phenyl- 1,2,4-thiadiazolyl, useful as nematocides.

2 Claims, No Drawings B18 (3 ,4,4-TRIFLUORO-3-BUTENYL) SULFIDE AS A NEMATOCIDE This application is a division of copending application Ser. No. 490,664 filed Sept. 27, 1965, now US Pat. No. 3,513,172.

This invention relates to certain new and novel chemical compounds and to the utility of said compounds as effective nematocides. More specifically, this invention relates to compounds of the general formula wherein R is a member selected from the group consisting of chlorothiophenyl, thio-3,4,4-trifluoro-3-butenyl, 2-thio-4,4,tS-trimethyldihydropyrimidyl, 2-thiobenzoxazoyl, 2-thiobenzothiazolyl, 2-thio-4-alkylthiazolyl, S- 3 ,4,4-trifluoro-3-butenyl)-ethylenebis(dithiocarbamoyl), thiobenzyl, thionaphthyl, phthalimido, dithio- 3,4,4-trifluoro-3-butenyl, thiopyridyl, N-thiazolidyl dione, and 5-thio-3-phenyl-l ,2,4-thiadiazolyl.

The compounds herein contemplated can be prepared by various methods. One such general method of preparing the compound with bonding by mean of a thio group is the condensation of the appropriate thiol (R-SH) and 3,4,4-trifluoro 3-butenyl bromide, usually in the presence of an organic base, such as triethylamine. Similarly, compounds wherein bonding is through a heterocyclic nitrogencondensation is accomplished using the appropriate sodium or potassium salt of the heterocyclic nitrogen containing compound and 3,4,4-trifluoro-3-butenyl bromide. The reactions proceed readily in the liquid phase. The employment of an inert organic solvent is also useful, facilitating processing as well as agitation of the reactants. Temperatures that permit operation in the liquid phase and which are between room temperature and reflux temperature of the solvent, if one is'used, are employed. Preferably the reaction mixture is refluxed, usually at an elevated temperature.

It has been found that the compounds of the present invention are particularly effective as mematocides. They are effective in the control of mematodes when applied to a nematodal habitat.

The compounds of the present invention may be prepared in accordance with the following illustrative examples.

EXAMPLE 1 Preparation of P-Chlorophenyl 3,4,4-Trifluoro-3-Butenyl Sulfide.

In 200 ml. methanol was dissolved 14.4 g. of pchlorothiophenol. To this solution was added 25 g. of.

EXAMPLE 2 Preparation of Bis(3,4,4-Trifluoro-3-Butenyl) Ethylene-Bis(Dithiocarbamate).

Ethylene diamine (0.2 moles) and triethylamine (0.2 moles) were dissolved in 100 ml. of dioxane. Carbon disulfied (0.2 moles) was added dropwise with stirring at l0-20 C. Stirred at room temperature for 15 minutes after addition was completed, then heated to 40 C. for 15 minutes. To the reaction mixture was added 0.15 mole (28.4 g.) of 3,4,4-trifluoro-3-butenyl bromide. This was heated to C. for 2 hours. The reaction mixture was poured into water and extracted with benzene. The benzene solution was subsequently washed with water, dried over anhydrous calcium chloride and finally the benzene removed in vacuo. There was obtained 77.4 g. of the title compoundmn 1.5292.

EXAMPLE 3 Preparation of 3-Phenyl-5-(3,4,4-Trifluoro-3-Butenyl Thia) 1,2,4Thiadiazole.

3-Phenyl-1,2,4-thiadiazole thiol-5, 6.6 'g., were mixed with 9.5 g. of 3,4,4-trifluoro-3-butenyl bromide in 150 cc. of dioxane as solvent with 10.1 g. of triethylarnine as the catalyst. The reaction mixture was refluxed for 2% hours. Isolation of the title compound was in the same manner as in Example 2. There was obtained 8.8 g. of a dark oil 51 915687.

EXAMPLE 4 Preparation of N-(3,4,4-Trifluoro-3-Butenyl) 2,4- Thiazol-ldenedione. r

In 100 ml. of methanol there was dissolved l 1.7 g. of 2,4-thiazolidinedione. This was treated with 0.1 mole of sodium methoxide in methanol. To this solution was added 18.9 g. of 3,4,4-trifluoro-3-butenyl bromide. The resulting mixture was refluxed 2 hours. The solvent was then evaporated and the residue 'was taken up in benzene. The benzene solution was washed with water, dried over anhydrous calcium chloride, and the solvent evaporated. There was obtained 7.2 g. of the title compound, 3P 1.4678. Analysis of the infrared spectrum supported the proposed structure.

As previously mentioned, the herein described novel compositions produced in the above described manner are biologically active compounds which are useful and valuable in the control of various organisms. The compounds of the invention were tested as nematocides in the following manner.

Nematocide Evaluation Test. This test determines a candidates action on root-knot nematodes (Meloido-' gyne, sp.) in soil. One-pound portions of soil infested with root-knot nemotodes were placed in quart jars. The chemical to be tested was pipetted into the nematode-infested soil at various dilutions of from 55 to 1 part per million (ppm) or until activity was lost. After mixing the candidate compound into the soil, the soil was sealed for 48 hours. The treated soil was\then placed in paper containers and allowed to stand in a greenhouse one week for airing. At the end of this time a tomato plant was transplanted into the soil. The rootknot nematodes attack the tomato plant roots if they survived the chemical treatment, and cause swelling or knots on the roots. Four weeks after treatment the plant was removed from the soil and the roots inspected. The lowest concentration which prevented nematode development was recorded.

TABLE Column 1 Column II Compound Control (ppm) p-chlorophenyl 3,4,4-trifluoro- 3-butenyl sulfide 1.5360 50 bis(3,4,4-trifluoro-3-buteny1) sulfide 1i4087 2.5 2-( 3,4,4-trifluoro-3-butenylthio )-4,4,6-

trimethyldihydropyrimidine 1.4949 25 2-( 3,4,4-trifluoro-3 -butenylthio)benzoxazole 1.5385 (2.5) 2-( 3,4,4-trifluoro-3-butenyl thio)-benzothiazole 1.5863 (2.5) 2-( 3,4,4-trifluoro-3-butenylthio )-4-methylthiazole 1.5 385 1 bis( 3,4,4-trifluoro-3-butenyl) ethylene-bis(dithiocarbamate) 1.5 292 l) Phenyl 3 ,4,4-trifluoro-3- butenyl sulfide 1.5442 50 3-phenyl-5-( 3,4,4-trifluoro-3- butenylthia l ,2,4-thiadiazole 1.5687 (2.5) 3 ,4,4-trifluoro-3-butenyl benzyl sulfide 1.5120 25 3 ,4,4-trifluoro3-butenyl a-naphthyl sulfide 1.5805 (50) N-( 3 ,4,4-trifluoro-3 -butenyl) phthalimide (semi- (2.5)

solid) Bis( 3,4,4-trifluoro-3-butenyl) disulfide (liquid) (2.5) 2-( 3,4,4-trifluoro-3- butenylthio )-pyridine 1.5258 25 4-( 3,4,4-trifluoro-3- butenylthio )-pyridine 1.5471 (2.5)

N-( 3,4,4-trifluoro-3- butenyl) 2,4- thiazolidenedione partial control The compounds of the present invention may be used as effective nematocides and may be applied to a variety of ways at various concentrations. In practice the compounds are usually formulated with an inert nematocidal adjuvant, utilizing methods well-known to those skilled in the art, thereby making them suitable for application as dusts, sprays, or drenches. The amount applied will depend upon the nature of the nematode to be controlled and the rate of application may vary from 1 to 50 pounds per acre. One particularly advantageous way of applying the nematocidal composition comprising the adjuvant and an effective amount of a compound of the present invention is as a spray, drench or dust followed by incorporation.

Various changes and modifications may be made without departing from the spirit and scope of the invention described herein as well be apparent to those skilled in the art to which it pertains. It is accordingly intended that the present invention shall only be limited by the scope of the appended claims.

We claim:

1. A method of controlling nematodes comprising applying thereto a nematocidally effective amount of the compound bis 3 4,4-triflu o ro-3-butenyl sulfide.

2. A nematoci ai composition comprising an inert 

2. A nematocidal composition comprising an inert nematocidal adjuvant and a nematocidally effective amount of the compound bis(3,4,4-trifluoro-3-butenyl) sulfide. 